O-alkyl-o-alkylphenyl-s-alkoxyethyl-phosphorothiolates

ABSTRACT

O-alkyl-O-alkylphenyl-S-alkoxyethyl-phosphorothiolates of the formula   IN WHICH R1, R2 and R3 are lower alkyl radicals, X is halogen, M IS 0 TO 3, AND N IS 1 OR 2, WHICH POSSESS INSECTICIDAL AND FUNGICIDAL PROPERTIES, COMPOSITIONS CONTAINING SUCH PHOSPHOROTHIOLATES AND THE METHOD OF COMBATING INSECTS AND FUNGI USING SUCH PHOSPHOROTHIOLATES.

United States Patent Kishino et al.

[54] O-ALKYL-O-ALKYLPHENYL-S- ALKOXYETHYL- PHOSPHOROTHIOLATES [72]Inventors: Shigeo Kishino; Yasuo Yamada;

Akio Kudamatsu; Shozo Sumi, all of Tokyo; Kozo Shiokawa, Kanagawa, allof Japan [73] Assignee: Farbenfabriken Bayer Aktiengesellsehaft,Leverkusen, Germany [22] Filed: Sept. 14, 1970 [21] Appl. No.: 72,114

[52] US. Cl. ..260/950, 260/964, 260/973,

, 260/979, 424/217 [51] Int. Cl. ..C07f 9/12, AOln 9/36 [58] Field ofSearch ..260/950 [56] References Cited FOREIGN PATENTS OR APPLICATIONS624,475 9/ 1961 Italy ..260/950 [151 3,683,053 51 Aug. 8, 1972 PrimaryExaminer-Joseph Rebold Assistant Examiner-Anton H. SuttoAttorney-Burgess, Dinklage & Sprung [57] ABSTRACTO-alkyl-O-alkylphenyl-S-alkoxyethyl-phosphorothiolates of the formula RO 0 B n R2OCH2CHZS Xm l 1 Claims, No Drawings-ALKYL-O-ALKYLPHENYL-S-ALKOXYETHYL- .1 PHOSPHOROTHIOLATES The presentinvention relates to and has for its objects the provision of particularnew O-alkyl-O-alkylphenyl-S-alkoxyethyl-phosphorothiolates, e.g. thealkyl radicals are lower alkyl and the phenyl ring may contain one ortwo such radicals and up to three halogen atoms, which possessinsecticidal and fun gicida'l properties, active compositions in theform of mixtures of such compounds with solid and liquid dispersiblecarrier vehicles, and methods for producing such compounds and for usingsuch compounds in a new 'way especially for combating insects and fungi,with other and further objects becoming apparent from a study of thewithin specification and accompanying examples.

It has now been found in accordance with the present invention, that theparticular new O-alkyl-O-alkylphenyl-S-alkoxyethyl-phosphorothiolates ofthe formula ROCHzCHz S is reacted witha compound of the formula Xm II)or in process variant (b) a compound of the formula R\ X... P"

is reacted with a compound of the formula I-Ial-CI-l CI-l OR v in whichR, R R, X, m and n have the same meanings as above, M is hydrogen, ametal equivalent or ammonium, M is a metal equivalent or ammonium andHal is halogen.

Advantageously in accordance with the present invention, in the variousformulas set forth herein:

R, R R are alkyl of one to four carbon atoms, for example methyl, ethyl,nor iso-propyl, n-, iso-, sec.- or tert.-butyl radical. R is preferablymethyl or ethyl, R is preferably methyl, ethyl, or n-(or iso-)propyl, Ris preferably methyl;

X, which is halogen, such as chlorine, bromine, fluorine or iodine, ispreferably chlorine or bromine;

M, which is hydrogen, ammonium or a metal, such as sodium, potassium,lithium, etc., is preferably hydrogen, sodium, potassium or ammonium; I

M, which is ammonium or a metal, such as sodium, potassium, lithium,etc., is preferably sodium, potassium or ammonium;

m, is 0 to 3, preferably 0 to 2, n, is l or 2 and Hal, which is halogensuch as chlorine, bromine, fluorine or iodine, is preferably chlorine,bromine.

Surprisingly, the particular new phosphorothiolates of formula (1) aboveaccording to the present invention exhibit broad activity against bothinsect pests and harmful fungi. These compounds are also-active againstmites which are resistant to organic phosphorus chemicals. Furthermore,as these compounds are free from heavy metals such as that in organicmercury chemi cals, there is no need to worry about a residual toxicityin harvested crops. Another advantage of these compounds is that theyexhibit low mammalian toxicity compared to Parathion.

The general process for the preparation of the instant compoundspursuant to process variant (a) is illustrated by the following reactionscheme:

R 0 0 R n i Ha1 Mo 1 11 0011201428 X".

R10 0 R n r-o-Q M-Hal 1 R20 omcliz s X...

in which R, R R, X, M, Hal, m and n have the same meanings as above.

The O-alkyl.-S-(2-alkoxy)ethyl thiolphosphoryl halide of formula (II)which is the starting material according to process variant (a), may beprepared according to conventional methods, for example, by treatingS-(2-alkoxy) ethyl thiolphosphoryl dihalide with a corresponding alcoholwith the use of an inert solvent or diluent. This reaction may becarried out in the presence of an acid-binding agent or by using a metalsalt of the corresponding alcohol instead of the acid-binding agent.

As examples of O-alkyl-S-(2-alkoxy)ethyl thiolphosphoryl halidesrepresented by the said general formula (II) which may be used there arementioned:

O-methyl-S-(2-ethoxy)ethylthiolphosphorylchloride,

O-ethyl-S-(Z-methoxy)ethylthiolphosphorylchloride,

O-ethyl-S-(2-ethoxy)ethylthiolphosphorylchloride,

O-ethyl-S-[2-n(or iso-)-propoxylethylthiolphospho ryl-chloride,

O-ethyl-S-(2-n-butoxy)ethylthiolphosphorylchloride O-n-butyl-S-(Z-ethoxy)ethylthiolphosphorylchloride and the like.

As examples of phenols of the formula (III) which may be used asstarting materials per se or in the form of their salts, such as sodium,potassium or ammonium, there are mentioned:

2-(3- or 4-)cresol,

2-iso-propylphenol,

2-sec.-butylphenol,

4-tert.-butylphenol,

2,4-dimethylphenol,

3,4-dimethylphenol,

3,5-dimethylphenol,

2-iso-propyl-5-cresol,

2-chloro-4-cresol,

2-chloro-6-cresol,

4-chloro-2-cresol,

4-chloro-3-cresol,

2-chloro-4-tert.-butylphenol,

3,5-dimet.hyl-4-chlorophenol,

2,4-dichloro-6-cresol, and the like.

The reactants may be reacted directly or in the presence of an inertsolvent or diluent including aliphatic or aromatic hydrocarbons (whichmay be halogenated), for example benzine, chlorinated methylene,chloroform, carbon tetrachloride, benzene, chlorobenzene, toluene,xylene, etc.; ethers, for example diethyl ether, dibutyl ether, dioxane,tetra-hydrofurane, etc.; aliphatic alcohols or ketones with low boilingpoints, for example methanol, ethanol, isopropanol, acetone, methylethyl ketone, methyl isopropyl ketone, methyl iso-butyl ketone; loweraliphatic nitriles such as acetonitrile, propionitrile; and the like.

The reaction may be carried out in the presence of an acid-bindingagent. For this purpose, alkali metal car-bonates, bicarbonates andalcoholates, such as potassium carbonate and sodium methylate andethylate and tertiary amines of aliphatic hydrocarbons, aromatichydrocarbons and heterocyclines such as triethyl amine, diethyl aniline,pyridine, and the like, can be used.

The reaction can be carried out within a fairly wide temperature range,but in general at temperatures from about to 110 C, and preferably fromabout 10 to 80 C.

The general process pursuant to variant (b) is illustrated by thefollowing reaction scheme:

D 0/ 'M Hal-CHzCHz-O-R R10 0 R3,, v11

ll /PO M- Hal R3 0 CH2 CHQS Xm (I) wherein R, R R X, M, m and n have themeanings given above.

The O-alkyl-O- alkyl -phenylthiophosphoric acid salt of formula (IV)which is the starting material according to variant (b) may be preparedaccording to conventional method, for example, by treating an O-alkyl-O-substituted-phenylthionophosphoryl chloride with an alkali metalhydroxide. The O-alkyl-O-substitutedphenylthiophosphoric acid salt thusobtained may be used after separation, or it may be directly reactedwith the 2-alkoxy-ethyl halide of formula (V) to produce the desiredproduct.

As examples of O-alkyl-O- alkyl -(or unsubstituted)-phenylthiophosphoric acid salts which may be used there are mentioned:

Potassium, sodium or ammonium salts of:

O-ethyl-O-( 2-iso-propyl O-ethyl-O-(2-sec.-butyl)-,

O-ethyl-O-(4-tert.-butyl)-,

O-ethyl-O-(2,4-dimethyl)-,

O-ethyl-O-(3,4-dimethyI)-,

O-ethyl-O-(3,5-dimethyl)-,

O-ethyl-O-(2-iso-propyl-5-methyl),

O-ethyl-O-(2-chloro-4-methyl)-,

O-ethyl-O-(2-chloro-6-methyl)-,

O-ethyl-O-(2-methyl-4-chloro)-,

O-ethyl-O-(3-methyl-4-chloro)-,

O-ethyl-O-(2-chloro-4-tert.-butyl)-,

O-ethyl-O-(3,5-dimethyl-4-chloro)-,

O-ethyl-O-(2,4-dichloro-6-methyl)-,

O-n-butyl-O-( 3-methyl-4-chloro O-n-butyl-O-(2,4-dichloro-6-methyl)-,

O-methyl-O-(4-chloro-3,5-dimethyl)-,

O-methyl-O-(4-tert.-butyl)-phenylthi0phosphoric acid, and the like.

As examples of 2-alkoxyethylhalides of formula (V), the other startingmaterial in process variant (b), the following are mentioned:

2-methoxyethyl bromide,

2-ethoxyethyl bromide,

2-n-(or iso-)propoxyethyl bromide,

2-n-butoxyethyl bromide, the corresponding chlorides or iodides, and thelike.

In this process variant, the reactants may be reacted directly, or inthe presence of an inert solvent or diluent.

This reaction can be carried out within a fairly wide temperature range,but in general at temperatures from about 0 to 100 C, and preferablyfrom about 30 to C.

Significantly, the active compounds according to the present inventionshow excellent insecticidal properties and, therefore, they areapplicable to the control of various kinds of insect pests, such assucking insects, biting insects and insect pests parasitic on plants.More precisely, these esters are effectively used as insecticidesagainst agricultural insect pests, such as Coleoptera, Lepidoptera,Aphidae Orthoptera, lsoptera, Acarina and Nematodes. These esters areeffectively used as plant protection agents, especially against riceinsect pests, such as rice stem borers, rice greenand leaf-hoppers aswell as other insect pests of fruit trees and vegetables. Furthermore,the compounds are characterized by excellent residual effectiveness whenused as insecticides in the control of hygienic and storage pests, suchas flies, cockroaches, mosquitoes and gnats.

Moreover, the phosphoric acid esters of formula (I) efiectively kill orinhibit the reproduction of plant pathogenic fungi, and therefore theyare applicable to the control of plant diseases caused by various kindsof fungus. These esters are effectively used as fungicides against plantdiseases caused by Archimycetes, Phycomycetes, Ascomycetes,Basidiomycetes, and Fungi lmperfecti. These esters are particularlyuseful against plant pathogenic fungi of rice, fruit trees andvegetables, with outstanding effects.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi.),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus korschelti), the mealyapple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleander scale (Aspidiotushederae) and the soft scale (Lecanium hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (Thysanoptera), such asHercinothrips femoralis, and bugs,- for example the beet bug (Piesmaquadrata), the cotton bug (Dysdercus intermedius), the bed bug (CimeQxlectularius), the assassin bug (Rhodnius prolixus) and Chagas bug(Triatoms infestans) and, further, cicadas, such as Euscelis bilobatus,and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all thereshould be mentioned butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plutella maculipennis), the gypsy moth (Lymantriadispar), the brown-tail moth (Euproctis chrysorrhoea) and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestrabrassicae) and the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumafa) thegreen oak tortrix moth (Tortrix vlridana), the fall armyworm (Laphygmafrugiperda) and cotton worm (Prodenia litura), the ermine moth(Hyponomeuta padella), the Mediterranean flour moth (Ephestia Kuhniella)and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein arebeetles (Coleopters), for example the granary weevil (Sitophilusgranan'us Calandra granaria), the Colorado beetle (Leptinotarsadecemlineata), the dock beetle (Gastrophysa viridula), the mustardbeetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius-Acanthoscelides obtectus), the leather beetle (Dennestes fn'schi), thekhapra beetle (Trogoderma granan'um) the flour beetle (Triboliumcastaneum), the northem corn billbug (Calandra or Sitophilus zeamais),the drugstore beetle (Stegobium paniceum), the yellow mealworrn(Tenebrio molitor) and the sawtoothed grain beetle (Oryzaephilussun'namensis), and also species living in the soil, for examplewireworms (Agriotes spec.) and larvae of the cockchafer (Melolonthamelolontha); cockroaches, such as the German cockroach (Blattellagermaru'ca), American cockroach (Periplaneta americana), Madeiracockroach (Laucophaea or Rhyparobia madeirae), Oriental cockroach(Blatta orientalis), the giant cockroach (Blaberus giganteus) and theblack giant cockroach (Blaberusfuscus) as well as Henschoutedeniaflexivitta; further, Orthoptera, for example the house cricket (Achetadomesticus); termites such as the eastern subterranean termite(Reticulitermes flavipes) and l-lymenoptera such as ants, for examplethe garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Fanm'a canicularis), the black blow fly (Phormia aegina) andbluebottle fly (Calliphora erythrocephala) as well as the stable fly(Stomoxys calcitrans); further, 'gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius Tetranychus althaeae or Tetranychusurticae) and the European red mite (Paratetranychus pllosus Panonychusulmi), blister mites, for example the currant blister mite (En'ophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata); and the like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, inert gaseous aerosolpropellants, and the like. These are prepared in known manner, forinstance by extending the active compounds with conventional pesticidedispersible liquid diluent carriers and/or dispersible solid carriersoptionally with the use of carrier vehicle assistants, e.g. conventionalpesticide surface-active agents, including emulsifying agents and/ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents. Thefollowing may be chiefly considered for use as conventional carriervehicles for this purpose: inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, etc.), halogenated, especially chlorinated,aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g.petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylenechloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol,etc.), amines (e.g. ethanolarnine, etc.), ethers, ether-alcohols, (e.g.glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.)and/or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g. kaolins, alumina,silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents,-for this purpose: emulsifying agents, suchas non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.) and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides andinsecticides, or rodenticides, fungicides, herbicides, bactericides,etc., if desired, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95 percent byweight, and preferably 05-90 percent by weight, of the mixture, whereascarrier composition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0005-20 percent,preferably 0.005-5 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (1) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible carrierliquid such as an inert organic solvent and/or water preferablyincluding a surface-active effective amount of a carrier vehicleassistant, e.g. a surface-active agent, such as an emulsifying agentand/or a dispersing agent, and an amount of the active compound which iseffective for the purpose in question and which is generally betweenabout 0.0005-95 percent, and preferably 0.005-95 percent, by weight ofthe mixture.

Dosage amounts are generally from -1,000 g, preferably 40-600 g ofactive compound per 10 ares. However, in special cases, it is possibleto exceed or reduce the amount and this may sometimes be necessary.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95 percent by weight of activecompound or even the 100 percent active substance alone, e.g. about20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects and fungi, andmore particularly methods of combating at least one of insects and fungiwhich comprises applying to at least one of correspondingly (a) suchinsects, (b) such fungi, and (c) the corresponding habitat thereof, i.e.the locus to be protected, a correspondingly combative or toxic amount,i.e. an insecticidally or fungicidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 CrIIsC CzH4S 28.5 g of the potassium salt of O-ethyl-O-(2,4-dimethylphenyl) thiophosphoric acid are dissolved in ml of alcohol. 16 gof 2-ethoxyethyl bromide are added to the resulting solution. Themixture is heated at 70C with stirring for 3 hours. After separation ofthe inorganic salt produced with filtration, the alcohol is distilledoff and the residue is dissolved in benzene. The benzene solution iswashed with water and a 1 percent carbonate solution and it is driedover anhydrous sodium sulphate. Upon distilling off the benzene, 22 g ofO- ethyl-O-(2,4-dirnethyl-phenyl)S-(2-ethoxyethyl)phosphorothiolate areobtained under reduced pressure distillation. B.p. 147 153C/0.08 mml-Ig,n 1.5129.

EXAMPLEZ CH CzIIsO o J (35) 0 Q Cz1I5OCzII4S 14.3 g of 4-chloro-3-cresolare dissolved in 150 ml of benzene and 10.1 g of triethylamine are addedto the resulting solution. 23.3 g of S-(2-ethoxyethyl)-O-ethylthiolphosphorylchloride are added to the mixture at below 10C whilestirring. The reaction mixture is stirred for a while at roomtemperature after completion of the addition and then it is heated to 6065 C for 3 hours with stirring. When the reaction is complete, thereacted mixture is washed sequentially with water, a 1 percenthydrochloric acid solution, a 1 percent sodium carbonate solution andagain water, and then it is dried over anhydrous sodium sulphate. Upondistilling off the benzene, distillation of the residue under reducedpressure gives 24 g of O-ethyl-O-(4-ch1oro-3-tolyl)-S-(Z-ethoxyethyl)phosphorothiolate. B.p.151-l53C/0.15 mml-Ig, n,," 1.5260.

EXAMPLE 3 The following compounds are prepared according to methodsanalogous to those of Examples 1 and 2. The Table identifies thecompounds by giving the meanings of the various variables in formula(I).

9 C 11,, C H-,-i 2-C,l-1 l49-l55/0.07 (1.5036) --i 10 C 11 C l-1 2-C.H,144-149/0.l (1.5070) -Sec. 11 C,l-1 C,H,-i 2C H, l45-146/0.1 (1.5045)sec. 12 CH: C,H 4-C l-l, 135-142/0.1 (1.5174) I -tert. 13 C,l-l C 11 4-C H, 143-150/0.2 (1.5076) -46". l4 C,H CH 2,4(CH:): l45151/0.1 (1.5167)15 C,l-l,, CJ-l, 2,4-(CH,), l47-153/0.08 (1.5129) 16 CJ-l, C,H-,n2,4-(CH,), 147-157/0.1 (1.5089) 17 CJI, C,H-,-i 2,4-(CH;): l42-l48/0.05(1.5070) 18 C ll C H,n 2,4(CH,), 149-l54/0.05 (1.5053) 19 C H C,H3,4(Cl-1,) 157l63/0.1 (1.5151) 20 C 11 C;H-,n 3,4-(CH,), l59-165/0.1(1.5109) 21 C 11,, C,H i 3,4(CH,), l67l72/0.l5 (1.5098) 22 (41-1; C 11LS-(CH 137-144/0.l5 (1.5109) 23 C 11,, C,1-1 -i 3,5(CH,), 154-158/0. 15(1.5062) 24 CJ-l, C H, 3-'-CH -,,6 156161/0.06 (1.5082) C,H-,-i 25 C 11CH, 4-CH, 2Cl 160-l70/0.2 (1.5269) 26 C,H,, C,H, 4-CH, 2Cl 133-140/0.1(1.5221) 27 C,H C,-,H-,n 4CH 2Cl 140l48/0.05 (1.5194) 28 CM, C,H-,i4-CH, 2-Cl 149l57/0.1 (1.5181) 29 CJI; C.H,-n 4-CH, 2Cl l57-166/0.05(1.5151) 30 C,H C 11,, 6-CH, 2C1 l49-156/0.1 (1.5209) 31 C,H, C,H 2-CH;4-Cl 145153/0.1 (1.5219) 32 C 11, C,H-,-n 2CH, 4Cl 148-152/0.l (1.5189)33 C l-1 C;,H i 2-CH, 4Cl 150-155/0.1 (1.5170) 34 C H, CJ-l, 3--CH, 4Cl159-165/0.1 (1.5171) n 35 C,H, C 11,, 3--CH, 4-C1 15ll53/0.15 (1.5260)36 C 11,, C,H n 3CH 4-C1 l6l-165/0.15 (1.5200) 37 C,H C,H-,i 3-CH, 4-Cl145-153/0.1 (1.5179) 38 CH, C 11,, 3,5 4-Cl 148-153/0.15 (1.5362) s)z 39C 11; C,H 3,5 4Cl 1S0-159/0.05 (1.5231) 40 C,H C;H n 3,5 4Cl 161169/0.1(1.5209) a): 41 C,H C,H-,i 3,5 4-C1 148-151/0.05 (1.5191) 42 CJl, C l-16-CH, 2,4 l52-l59/0.1 (1.5331) Cl, 43 C l-l', C,H -n 6-CH, 2,4163-173/0.1 (1.5314) Cl, 44 C,H C,H',i 6-CH, 2,4 15516l/0.2 (1.5291) Cl,45 C 11, C 11 6-CH; 2,4 167-171/0.l5 (1.5260) Cl, 46 C 11,, C,H 4-C H,2CL 159l6l/0.15 (1.5162) IB\1 47 C,H,, C,H-,n 4-C H, 2Cl -l60l66/0.1(1.5160) tert 48 C,H,, C,H-,i 4-C H. 2Cl 153-157/0.08 (1.5132) EXAMPLE 415 parts by weight of compound 35'of Table 1, parts by weight of amixture of diatomaceous earth and clay (1:5) and 5 parts by weight of anemulsifier (i.e. polyoxyethylene alkylaryl ether) are mixed and crushedto prepare a wettable powder. This formula tion may be diluted withwater to the desired concentration and then be used as aready-to-use-preparation.

EXAMPLE 5 30 parts by weight of compound 7 of Table 1, 30 parts byweight of xylene, 30 parts by weight of Kawakasol (an aromatichydrocarbon with a boiling range of 150 to 200 C.) and 10 parts byweight of the emulsifier Sorpol (i.e. polyoxyethylene alkylaryl ether)are mixed and stirred to prepare an emulsifiable concentrate. Thisformulation may be diluted with water to the desired concentration andthen used as a ready-touse-preparation.

EXAMPLE 6 To a mixture consisting of 10 parts by weight of Compound 46of Table 1, 10 parts by weight of bentonite, 78 parts by weight of amixture of talc and clay (1:3) and 2 parts by weight of lignin sulfate,25 parts by weight of water are added and the mixture is firmly kneaded.It is finely cut into granules of 0.5 to 1.5 mm diameter by means of agranulating machine. The granules are then dried at a temperaturebetween 40 to 50 C to obtain a granular formulation. This formulationmay directly be applied to the soil.

EXAMPLE 7 2 parts by weight of Compound 28 of Table l and 98 parts byweight of a mixture of talc and clay (1:3) are mixed and crushed toprepare a dust. This formulation To prepare a suitable preparationpreparation of the active compound, 1 part by weight of the activecompound was thoroughly mixed with the stated amount of solvent and thestated amount of emulsifier. The obtained emulsifiable concentrate wasthen diluted with water to the desired concentration.

Leaves of sweet potato were dipped in the diluted preparation of theactive compound and then dried and put in a Petri dish of 9 cm diameter.10 tobacco cutworrn larvae were then placed in the dish. The dish waskept at a temperature of 28 C. 30 test insects'were used altogether foreach active compound at each concentration.

After 24 hours, the number of dead insects were counted and themortality rate was calculated as a percentage. 100 percent means thatall insects were killed, 0 percent means that none of the insects werekilled.

The average results obtained are shown in the Table TABLE 2 Results oftest against tobacco cutworm (Prodenia litura) larvae Compound Mortalityof Table l at a concentration of acti ve ingredient of 1,000 ppm 300 ppm100 ppm 1 100% 100% 40% 2 100 100 50 3 100 100 20 4 100 100 40 5 100 10050 6 100 100 80 7 100 100 100 8 100 100 90 9 100 100 90 10 100 100 30 11100 100 50 12 100 100 70 13 100 100 80 14 100 70 6O 15 100 100 70 16 100100 100 17 100 100 100 18 100 100 80 19 100 100 80 20 100 100 100 21 100100 100 22 100 100 100 23 100 100 90 24 100 90 20 25 100 60 26 100 10080 27 100 100 40 28 100 100 70 29 100 90 40 30 100 100 100 31 100 100100 32 100 100 100 33 100 100 100 34 100 70 10 35 100 100 100 36 100 10037 100 100 100 38 100 100 39 100 100 100 40 100 100 80 41 100 100 100 42100 100 100 43 100 100 100 44 100 100 100 45 100 100 46 100 100 100 47100 100 90 48 100 100 100 Control A 100 80 40 Control B 100 90 10Notes: 1. Control A: 0,0-dimethy1-O-( 3-methyl-4-nitrophenyl)thiophosphatc (Sumithion) 2. Control B:O-ethylO-(4-chlorophenyl)-S(2-ethylthioethyl)- phosphorothiolate EXAMPLE9 Controlling eflect test against carmine mite (Tetranychus telarius)After 10 days, the controlling efiect was evaluated according to thefollowing scale:

3 The proportion of surviving adult and young miles as well as eggs is 0percent.

2 The proportion of surviving adult and young mites as well as eggs isless than 5 percent of that of the non-treated group.

1 The proportion of surviving adult and young mites as well as eggs is5-50 percent of that of the non-treated group.

0 The proportion of surviving adult and young mites as well as eggs ismore than 50 percent of that of the non-treated group.

The average results obtained are shown in the Table 3 below.

TABLE 3 Results of test against carmine mite Test against rice stemborer (Chilo supperssalis) larvae Egg masses of rice stem borer wereattached to paddy rice plants of tillering stage, 3 to 5 of which beingin one pot of about 12 cm diameter. 7 days after the hatching of theeggs, such plants were sprayed with the preparation of the activecompound (prepared in the same manner described in Example 8) untildripping wet. 3 pots were used for each active oompound at eachconcentration. The pots were placed in a greenhouse and the temperaturewas maintained at 25 C. Three days after the spraying, the stems of theplants were split by hand and the numbers of surviving dead insects inthe stems were counted and the mortality rate was calculated as apercentage. percent means that all the insects were killed, 0 percentmeans that none of the insects were killed.

The average results obtained are shown in the Table 4 below.

TABLE 4 Results of test against rice stem borer larvae Compound of Table1 Concentration Mortality 3 250 ppm 100% 5 250 100 6 250 100 7 250 96.18 250 100 9 250 95.8 13 250 100 14 250 100 15 250 100 16 250 100 17 250100 19 250 100 20 250 100 21 250 100 25 250 100 l3 14 26 250 100 T ABLE6 27 250 100 23 250 06.9 Results of test agalnst German cockroaches 29250 96.1 31 250 100 Compound Mortality at a concentration of 32 250 100of Table 1 L000 ppm 100 ppm 33 250 81.8 35 250 100 37 250 100 3 100%100% 42 250 100 5 100 4a 250 100 6 100 Control c 250 95 7 100 Control I)250 I00 8 1 I00 Notes: 1. Control C:0,0-dimethyl-2,2,2-trichloro-l-hydroxyethylphosphonate (Dipterex) '8 r00 2 Control D: 0,0-dimethyl-O-[4-(methylthio-3-methyl)phenl9 100yl]thiophosphate (Le-Baycid) l 5 [00 21 100 EXAMPLE l1 1 100 26 100 Testagainst the adult house-fly (Musca domestica) '88 1 ml of the dilutedpreparation of the. active com- 20 g? pound (prepared in the same mannerdescribed in Ex- 32 100 100 ample 8) was adsorbed onto filter paperplaced in a :88 Petr1 dish of 9 cm diameter. 10 mature female adult 37100 100 house flies were then placed in the Petri dish. The dish waskept at a temperatureof 28 C. test insects were 25 EXAMPLE 13 usedaltogether for each active compound at each con- I centrafiom Testagainst r1ce blast (Pmculana oryzae pot test) After 24 hours number bfdead insects was Solvent: 5 parts by weight of aceton counted and themortality rate was calculated as a per- Emulsifier: 1 part by weight ofcentage. 100 percent means that all insects were killed, 30 Pdymqemylenealkylaryleth" 0 percent means that none of the insects were killed. Toprepare a suitable preparation of the active com- The average resultsobtained are shown in the Table pound, 1 part by weight of the activecompound was 5 below. thoroughly mixed with the stated amount of solventand the stated amount of emulsifier. The obtained TABLE 5 emulsifiableconcentrate was then diluted with water to the desired concentration.Results of test agamst the adult house-fly a Test of Protective. Effect:Compound Mortality at a concentration of Rice plants (Jukkoku 'variety)were grown in pOtS Table] 1100) PP'" PP' each having a diameter of 12cm. In the tillering stage, 4 such plants were sprayed with thepreparation of the 3 100% 100% active compound until dripping wet. g 183g3 For the next 2 days, the treated pots were placed in a 7 100 chamberat a temperature of 25 C and a relative ats 100 20 mospheric humidity ofabout 100 percent. Twice dur- 9 100 100 14 100 w mg th1s me, such plantswere inoculated by spraymg 15 100 with a suspension of cultured sporesof Piricularia 16 100 1g oryzae 17 100 1a 100 30 Seven days afterInoculation, the degree of infestag :33 Kg tion was determined byapplying a scale ranging from 0 25 100 90 y p y to 5, and the protectivevalue of each particular active 26 100 30 compound against Piriculariaoryzae was determined in 27 100 100 r 28 100 100 accordance with theformula below. 29 100 30 At the same time, the phytotoxity against riceplants 31 90 was determined. 32 100 100 33 100 100 Degree of infestedarea of leaf 35 I00 100 infestation in of total leaf 37 p 100 100 DDT(Control) 100 a 20 y-BHC (Control) 100 90 0 0 i it; EXAMPLE 12. 3 1040*4 20 40 Test agalnst German cockroaches (Blatella germamca) 5 40 or moreThe test was carried out in the same manner as that an kro ch instead ofof Example usmg the Germ coc a Degree of infestation of treated plantsthe house fly. X

The average results obtained are shown in the Table Degree f i f t ti f6 below. treated plants Protective value TEST EXAMPLE 14 Test againstrice sheath blight Pellicularia sasakii pot test) Rice plants (Kinmazevariety) were grown in pots each having a diameter of 12 cm. In thebeginning of the tillering stage, the preparation of active compound(prepared in the same manner described in Example 13) was sprayed ontothe test plant until dripping wet.

On the next day, the schlerotium of Pellicularia sasakii, obtained byculturing for days in a wheat culture medium, was inoculated onto theroots of the plants. The pots were then maintained for 8 days in achamber at a temperature between 28 and 30C and a relative atmospherichumidity of at least 95 percent.

The infestation of the stems was determined and characterized by thevalues n to n having the meaning given below.

The degree of infestation was determined by means of the formula (1) andthe protective value of each compound was calculated in accordance withthe formula(2):

wherein N the number of the total stems examined n the number ofnon-infested stems n the number of stems infested up to the first leaf(from the bottom) n the number of stems infested up to the second leaf(from the bottom) n the number of stems infested up to and above thethird leaf (from the bottom) The active compounds tested, theirconcentrations and the average results can be seen from the followingTable 7.

TABLE 7 Results of tests against rice blast and sheath blight Notes: 1.Phytotoxicity: means that no ill effect on the growth of rice plants wasseen. 2. Control E: 0,0-diisopropyl-Sbenzylthiolphosphate (IBP) It willbe appreciated that the instant specification and examples are set forthby way of illustration and not limitation and that various modificationsand changes may be made without departing from the spirit and scope ofthe present invention.

What is claimed is:

l. Phosphorothiolates of the formula in which R, R and R are lower alkylradicals,

X is halogen,

m is 0 to 2, the halogens when present being in the 2- ,4- or2,4-p0sitions and n is l or 2.

2. A phosphorothiolate according to claim 1, wherein R, R and R arealkyl of one to four carbon atoms, X is chlorine or bromine, m is 0 to2, and n is l or 2.

3. A phosphorothiolate according to claim 1, wherein R is alkyl of oneto two carbon atoms, R is alkyl of one to three carbon atoms, R ismethyl, X is chlorine, m is 0 to 2 and n is 1 or 2.

4. Compound according to claim 1 wherein such compound isO-ethyl-O(3-tolyl)-S-(2-ethoxyethyl)phosphorothiolate of the formula(321150 ClIzClIzS 5. Compound according to claim 1 wherein such compoundis O-ethyl-O-(2-isopropyl-phenyl)-S-(2- isopropoxyethyl)phosphorothiolate of the formula 1) lC3lI70CIIzClI1S (9) 6. Compoundaccording to claim 1 wherein such compound isO-ethyl-O-(3,4-dimethylphenyl)-S-(2-npropylethyl)phosphorothiolate ofthe formula on, (auto 0 I i on, n--( );,lI ()(1ll Cll S 20 7. Compoundaccording to claim 1 wherein such 0 compound isO-ethyl-O-(4-chloro-2-tolyl)-S-(2-npropoxyethyl)phosphorothiolate of theformula on3 ohm) o "(11.11 0ommnsw 0 -01 8. Compound according to claim1 wherein such compound is O-ethyl-O-(4-chloro 2-tolyl)-S-(2-isopropoxyethyl )phosphorothiolate of the formula CID:

Q P4) "(:1 i mnmoihonzs 9. Compound according to claim 1 wherein suchcompound isO-ethyl-O-(4-chloro-3-tolyl)-S-(2-ethoxyethyl)phosphorothiolate of theformula l7 l8 CQHSO 11. Compound according to claim 1 wherein such 0 C1compound is O-ethyl-O-(4,6-dichloro-2-tolyl)-S-(2-lsopropoxyethyl)phosphorothiolate 0f the formula CzHOCH2CHgS (as 10.Compound according to claim 1 wherein such 5 O compound isO-ethyl-O-(4-chloro-3-toly])-S-(2- '2 J \Hisopropoxyethyl)phosphorothiolate of the formula '0 Q H CH3 (37)FVUQIHOCHQUHZSI C2H O\(fi /1 o @-c1 l0 CaHv0CHzCH2S a: a:

UNITED STATES PATENT OFFICE CERTIFECATE 0F CORRECTION Patent No.3,683,053 Dated August 8, 1972 Inventor) Shigeo Kishino et a1.

It is certified that error appears in the aboveidentified patent andthat said Letters Patent are hereby corrected as shown below:

On the cover sheet insert Claims priority,

application Japan, Sept. 17, 1969 Sho 4 4-73204 Signed and sealed this26th day of March 1974.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents FORM po'wso USCOMM-DC scan-P60 i [1.5. GOVERNMENT PRINTINGOFFICE I95, 0-355-38,

2. A phosphorothiolate according to claim 1, wherein R1, R2 and R3 arealkyl of one to four carbon atoms, X is chlorine or bromine, m is 0 to2, and n is 1 or
 2. 3. A phosphorothiolate according to claim 1, whereinR1 is alkyl of one to two carbon atoms, R2 is alkyl of one to threecarbon atoms, R3 is methyl, X is chlorine, m is 0 to 2 and n is 1 or 2.4. Compound according to claim 1 wherein such compound isO-ethyl-O-(3-tolyl)-S-(2-ethoxyethyl)phosphorothiolate of the formula 5.Compound according to claim 1 wherein such compound isO-ethyl-O-(2-isopropyl-phenyl)-S-(2-isopropoxyethyl)phosphorothiolate ofthe formula
 6. Compound according to claim 1 wherein such compound isO-ethyl-O-(3,4-dimethylphenyl)-S-(2-n-propylethyl)phosphorothiolate ofthe formula
 7. Compound according to claim 1 wherein such compound isO-ethyl-O-(4-chloro-2-tolyl)-S-(2-n-propoxyethyl)phosphorothiolate ofthe formula
 8. Compound according to claim 1 wherein such compound isO-ethyl-O-(4-chloro-2-tolyl)-S-(2-isopropoxyethyl)phosphorothiolate ofthe formula
 9. Compound according to claim 1 wherein such compound isO-ethyl-O-(4-chloro-3-tolyl)-S-(2-ethoxyethyl)phosphorothiolate of theformula
 10. Compound according to claim 1 wherein such compound isO-ethyl-O-(4-chloro-3-tolyl)-S-(2-isopropoxyethyl)phosphorothiolate ofthe formula
 11. Compound according to claim 1 wherein such compound isO-ethyl-O-(4,6-dichloro-2-tolyl)-S-(2-isopropoxyethyl)phosphorothiolateof the formula